Syntheses and Magnetic and Conductive Properties of New Low-Dimensional Complexes

新型低维配合物的合成及其磁性和导电性能

• 批准号: 10640547
• 负责人: HANDA Makoto
• 金额: $ 1.79万
• 依托单位: Shimane University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 1998
• 资助国家: 日本
• 起止时间: 1998 至 2000
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-10640547/
• 关键词: low-dimensional complexes; dinuclear complexes; phthalocyanine; metal-metal bond; bridging ligands; nitroxide radicals; p-quinones; pyrazine; 電導性; 磁性; ニトロキトラジカル; TCNQ; ニトロキシドラジカル; キノン

Phthalocyanines (Pcs) are well known to show remarkable increase in electrical conductivity on their partial oxidation, being originated from continuously stacking of the phthalocyanine rings based on the enhanced π-π interaction. However, the conductivity abruptly decreases when the temperature is lowered, which is explained in terms of Peierls-transition. In this research, a dinuclear copper (II) phthalocyanine ([CuPc(t-Bu)_3]_2) was newly prepared for investigation on ability of the dinuclear phthalocyanine complexes to get rid of the Peierls problem by giving rise to interaction other than the π-π one in the stacked structure. The observed intramolecular Pc-Pc interaction indicated that the dinuclear Pcs would be promising for developing low-dimensional materials in this way. However, no significant intramolecular magnetic interaction between the metal ions was observed although the interaction is considered to play an important role for the properties of the low-dimensional compou … More nds. The investigation on the other paramagnetic metal ions with dinucleating phthalocynine ligands will be performed.Polymer complexes have been prepared using dinuclear metal complexes M_2(O_2CR)_4 (M = Ru(II,III), Rh(II), Mo(II)) and various bridging ligands. The ruthenium (II,III) dimers have three unpaired electrons. Reactions with nitroxide radicals gave polymers of ruthenium (II,III) dimers axially linked by the radicals. The magnetic data showed strong interactions between the dimers and radicals, though an expected ferrimagentic property based on the alternated S=3/2 (for Ru_2) and S=1/2 (for nitroxide) arrangement was not observed. The rhodium (II) dimers were linked with pyrazine, 4, 4'-bipyridine, and 1, 4-diazabicyclo [2.2.2] octane. The polymer structure was confirmed by X-ray crystal analysis for the bipyridine complex. The molybdenum (II) polymers with p-quinones (9, 10-anthraquinone, 1, 4-naphthquionone, and 2, 6-dimethyl-1, 4-benzoquinone) were also prepared. The detailed analyses based on their X-ray structures indicated existence of interactions between the dimers and p-quinones. The above obtained results implies that the dimer complexes having metal-metal bonds are useful building blocks for metal-assembled complexes in combination with linkage ligands. Less

酞菁化合物（Phthalocyanines，Pcs）在部分氧化后导电性显著提高，这是由于酞菁环之间的π-π相互作用增强而导致的。然而，当温度降低时，电导率突然下降，这是根据Peierls转变来解释的。本研究首次合成了双核酞菁铜（[CuPc（t-Bu）_3]_2），并研究了双核酞菁铜配合物通过在叠层结构中引入π-π以外的相互作用来解决Peierls问题的能力。分子内Pc-Pc相互作用的研究表明，双核酞菁配合物在开发低维材料方面具有广阔的应用前景。然而，没有观察到明显的金属离子之间的分子内磁相互作用，尽管这种相互作用被认为对低维化合物的性质起重要作用。 ...更多信息 nds.以双核金属配合物M_2（O_2CR）_4（M = Ru（II，III），Rh（II），Mo（II））和各种桥联配体合成了高分子配合物。钌（II，III）二聚体具有三个未配对电子。与氮氧自由基的反应得到的聚合物的钌（II，III）二聚体轴向连接的自由基。磁性数据表明二聚体与自由基之间存在很强的相互作用，但没有观察到预期的基于S=3/2（对于Ru_2）和S=1/2（对于氮氧自由基）交替排列的亚铁磁性。铑（II）二聚体与吡嗪、4，4 '-联吡啶和1，4-二氮杂双环[2.2.2]辛烷连接。通过X-射线晶体分析证实了聚合物的结构。还制备了钼（II）与对苯醌（9，10-蒽醌、1，4-萘醌和2，6-二甲基-1，4-苯醌）的聚合物。基于它们的X-射线结构的详细分析表明，二聚体和对醌之间存在相互作用。以上获得的结果意味着具有金属-金属键的二聚体配合物是用于与连接配体组合的金属组装配合物的有用结构单元。少

项目成果

Makoto Handa: "Chain compounds of molybdenum(II) trifluoroacetate linked by p-quinones [Mo_2(O_2CCF_3)_4(p-quin)]_n"Bul.Chem.Soc.Jpn.. 71. 1811-1816 (1998)

Makoto Handa：“由对醌连接的三氟乙酸钼(II)的链状化合物 [Mo_2(O_2CCF_3)_4(p-quin)]_n”Bul.Chem.Soc.Jpn.. 71. 1811-1816 (1998)

Kuninobu Kasuga: "Oxygen-oxygenation of cyclohexene catalyzed by manganese (III), iron (III), and cobalt (II) complexes of tetra-tert-butylphthalocyanine in the presence of isobutylaldehyde"Inorg.Chem.Commun.. 2. 507-509 (1999)

Kuninobu Kasuga：“在异丁醛存在下，四叔丁基酞菁的锰 (III)、铁 (III) 和钴 (II) 络合物催化环己烯的氧氧化”Inorg.Chem.Commun.. 2. 507-

Makoto Handa: "Adduct polymers and dimers of rhodium (II) pivalate with pyrazine, 4,4'-bipyridine, 1,4-diazabicyclo [2.2.2] octane, triethylamine, and pyridine"Bull.Chem.Soc.Jpn.. 72. 2681-2686 (1999)

Makoto Handa：“新戊酸铑 (II) 与吡嗪、4,4-联吡啶、1,4-二氮杂双环[2.2.2]辛烷、三乙胺和吡啶的加合物聚合物和二聚体”Bull.Chem.Soc.Jpn..

Kuninobu Kasuga: "Kinetic study on oxidation of tetrachlorophenol using hydrogen peroxide and an iron (III) complex of tetrasulfonatophthalocyanine catalyst"Bull.Chem.Soc.Jpn.. 73. 939-940 (2000)

Kuninobu Kasuga：“使用过氧化氢和四磺基酞菁催化剂的铁 (III) 配合物氧化四氯苯酚的动力学研究”Bull.Chem.Soc.Jpn.. 73. 939-940 (2000)

Kuninobu Kasuga: "Determination of quenching process for the photoreduction of methyl viologen catalyzed by (sulfonatophthalocyaninato) zincate (II) in the presence of triethanolamine"Inorg.Chim.Acta.. 307. 164-166 (2000)

Kuninobu Kasuga：“在三乙醇胺存在下由（磺基酞菁）锌酸盐（II）催化的甲基紫精光还原猝灭过程的测定”Inorg.Chim.Acta.. 307. 164-166 (2000)